Use of fermentation residues as flow-enhancing agents in cementitious materials

ABSTRACT

Herein is disclosed an admixture, for concrete, gypsum panels, and other cementitious products, derived from fermentation still bottoms. The admixture typically comprises protein, glycerol, and lactate, as well as smaller amounts of other alcohols, sugars, and other organic acids. The admixture may be present as a solution (typically comprising about 30-50 wt % solids) or as a dry mixture. The admixture allows increased flow and reduced water use in concrete and gypsum slurries used in gypsum panel production. Concrete, cement, and gypsum premixes, ready-mixes, and poured structures are disclosed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to the fields of microbialfermentation and cementitious admixtures. More particularly, it concernsthe use of fermentation residues to improve the properties of concretesand similar products.

2. Description of Related Art

Fermentation is a well-known technique for producing a number ofcommercially relevant organic compounds, including, but not limited to,ethanol and organic acids. In fermentation, a microorganism, in manycases yeast, is grown in a fermentation vessel on a medium suitable forthe microorganism's growth. A commonly-used medium for yeast comprisesdextrose and corn steep liquor. During the course of fermentation, themicroorganism biomass increases and a commercially relevant targetproduct is generated. After microorganism growth is complete, the targetproduct is isolated, typically by one or more of distillation,crystallization, solvent extraction, and chromatographic separation.After recovery of the target product the microorganism biomass,non-fermentable components of the medium, and water-soluble compoundsgenerated by the microorganism remain in the fermentation vessel. Thesecomponents together may be referred to as “beer still bottoms” or“fermentation still bottoms.”

To dispose of beer still bottoms, producers frequently pass thismaterial to the animal feeds industry. This does capture some economicvalue from the material; however, this value is typically very low.Therefore, producers would prefer to capture more economic value frombeer still bottoms than is possible from animal feeds uses.

Concrete is a ubiquitous construction material, both in the UnitedStates and in most countries of the world. In the United States duringthe year 2000, roughly 440 million cubic yards of ready-mix concretewere produced. In order to save on the amount of water used, enhance theproperties of the concrete prepared therefrom, or both, about 90% of allready-mix concrete in the United States is treated with an admixture.Low range water reducing admixtures are often used at about 0.25 gal percubic yard. High range water reducing admixtures are often used at about1 gal per cubic yard. Assuming that these admixtures are produced assolutions comprising 50 wt % solids, annual admixture demand in theUnited States alone would be in the range of 50 million pounds to 100million pounds.

Therefore, it would be desirable to have a new and valuable use for beerstill bottoms or one or more components thereof It would also bedesirable to have cementitious compositions with improved flow andrelated properties without a concomitant increase in the amount of waterrequired in the cementitious composition. It is well known in the artthat increased water in the cementitious slurry will decrease theultimate strength of the hardened material.

Yoshizawa et al., U.S. Pat. No. 4,311,721, reports the extracting ofwater-soluble compounds from fermentation still bottoms and the use ofthe water-soluble compounds in a fermentation medium or an animal feed.

Willgohs, U.S. Pat. No. 5,662,810, discloses the use of dewatered beerstill bottoms as an animal feed.

Hamstra et al., U.S. Pat. No. 5,760,078, teaches the extraction ofpotassium salts from the water-soluble compounds of fermentation stillbottoms, and the use of such potassium salts as a fertilizer.

Sapienza, U.S. Pat. No. 6,315,919, reports the use of water-solublecompounds from beer still bottoms as a deicing agent.

SUMMARY OF THE INVENTION

In one embodiment, the present invention relates to a compositioncomprising a cementitious material and a fermentation residue.

In another embodiment, the present invention relates to a method ofpreparing a composition comprising a cementitious material and afermentation residue, the method comprising (i) growing a microorganismon a medium, to form at least a microorganism biomass and fermentationresidue; (ii) separating the fermentation residue from the microorganismbiomass; and (iii) combining the fermentation residue with thecementitious material, to form the composition.

In still another embodiment, the present invention relates to a methodof producing a cementitious structure, comprising (i) combining at leasta fermentation residue, a cementitious material, and water, to yield aslurry; (ii) forming the slurry into an unset cementitious structure;and (iii) setting the unset cementitious structure, to yield thecementitious structure.

In a further embodiment, the present invention relates to a composition,comprising a fermentation residue, water, and an inorganic materialdispersed in the water.

In yet a further embodiment, the present invention relates to a methodof preparing a composition comprising a fermentation residue, water, andan inorganic material dispersed in the water, the method comprising: (i)growing a microorganism on a medium, to form at least a microorganismbiomass and fermentation residue; (ii) separating the fermentationresidue from the microorganism biomass; and (iii) combining thefermentation residue with the water and the inorganic material, to formthe composition.

In still a further embodiment, the present invention relates to a methodof producing a paper structure containing an inorganic material,comprising: (i) combining a fermentation residue with water and aninorganic material, to yield a solution; (ii) treating the paperstructure with the solution, to yield a treated paper structure; and(iii) removing water from the treated paper structure, to yield thepaper structure containing the organic material.

The various embodiments of the present invention provide a new andvaluable use for fermentation residues. The present invention alsoprovides for cementitious compositions with improved flow and relatedproperties without a concomitant increase in the amount of waterrequired in the cementitious composition.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings form part of the present specification and areincluded to further demonstrate certain aspects of the presentinvention. The invention may be better understood by reference to one ormore of these drawings in combination with the detailed description ofspecific embodiments presented herein.

FIG. 1 shows a process flow diagram for the isolation of a fermentationresidue from a fermentation process.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The various embodiments of the present invention relate to afermentation residue and methods for its production and use.

Fermentation involves growing a microorganism on a medium, to form atleast a microorganism biomass and fermentation still bottoms comprisingwater-soluble compounds and insoluble compounds. A typical fermentationyields a target product, water, microorganism biomass, and water-solublecompounds. The microorganism biomass and water-soluble compounds maytogether be referred to as “corn stillage.” The remaining contents ofthe fermentation medium, after removal of the target product and themicroorganism biomass, may be referred to as a “fermentation residue” or“distillers solubles.”

The growing step can involve any microorganism and any medium known toone of ordinary skill in the art to be suitable for growing themicroorganism. Typical microorganisms useful in the method include, butare not limited to, yeast, other fungi, and bacteria, among others.Media appropriate for the growing of any particular microorganism willgenerally be well known in the art. The growing step will typically takeplace in a fermentor at a temperature, pressure, pH, duration, and otherparameters which allow the microorganism to grow to a desiredconcentration, typically a static concentration at the upper range of asigmoidal growth curve. During the growing step, a microorganism biomassand fermentation residue will form.

Also during the growing step, the microorganism biomass may produce atleast one target product, i.e. a desirable compound readily produced byand extractable from a microorganism biomass. Typically, themicroorganism is grown on the medium with the primary objective ofproducing a target product or compounds. However, this is not necessary.The target product or compounds produced will depend on themicroorganism and the medium. The microorganism can, but need not, be arecombinant organism capable of producing target products other thantarget products producible by the wild-type or nonrecombinantmicroorganism. In one embodiment, the microorganism is yeast. In oneembodiment, the target product is ethanol. In another embodiment, themicroorganism is a Corynebacterium (i.e., a bacterium of the genusCorynebacterium). In another embodiment, the target product is lysine.In one embodiment, the microorganism is a yeast and the at least onetarget product is ethanol. In another embodiment, the microorganism is aCorynebacterium and the at least one target product is lysine.

If at least one target product is produced by the fermentation, it isdesirable to remove the at least one target product, to retain themicroorganism biomass and the fermentation residue. If no target productis produced by the fermentation, then such a removal step will not benecessary. Removal of any target product can be performed by anyappropriate technique; most commonly, removal of any target product fromthe microorganism biomass and fermentation still bottoms can beperformed by one or more of distillation, crystallization, solventextraction, and chromatographic separation.

A subsequent step in the process is separating the fermentation residuefrom the microorganism biomass. In the separating step, after the targetproduct, if any, has been isolated, the fermentation residue isseparated from the microorganism biomass by one or more appropriatetechniques, such as filtration, evaporation (including evaporationassisted by the application of vacuum, heat, or both), centrifugation,and solvent extraction, among others. Typically, the microorganismbiomass and the fermentation residue are subjected to microfiltration.One or more membranes with pore sizes in the range of from about 50 nmto about 1500 nm are generally suitable. Upon microfiltration, thefermentation residue will generally be present in the permeate, and themicroorganism biomass will be present in the retentate. The fermentationresidue will generally comprise water-soluble compounds.

The steps described to this point, as exemplified in a typical butnon-limiting yeast ethanol fermentation, are shown in FIG. 1. A mediumis added from a medium source 100 to a fermentor 102. A yeast culture(not shown) is also added to the fermentor 102, and growth of the yeastis allowed. During this process, ethanol is produced. The medium, yeastbiomass, ethanol, and other components are then passed to a distillationtower 104, from which ethanol is extracted in fraction 106. In theconventional process known in the art, the yeast biomass 110 andfermentation residue 112 (collectively known as “beer still bottoms” or“BSB” 114) was processed to animal feed 108. In the present invention,beer still bottoms 114 are fed to a separating apparatus, such as one ormore microfiltration membranes 116, wherein the yeast biomass 110remains in the retentate 118, and the fermentation residue 112 passes tothe permeate 120. Alternative process flows and techniques and apparatususable therein are possible, as will be apparent to one of ordinaryskill in the art.

The fermentation residue can be used as-is. The concentration ofwater-soluble compounds in the fermentation residue will typically onlybe in the range of about 2% to about 10%. In many applications, it maybe suitable to prepare a more highly concentrated solution of thefermentation residue. Therefore, the method may further compriseconcentrating the fermentation residue prior to subsequent use thereof.Such concentration can be performed by evaporation, spray drying, or anyother appropriate technique known to one of ordinary skill in the art.

The method may further comprise the partial or complete removal of oneor more compounds from the fermentation residue.

The composition of the fermentation residue is complex and will dependon the microorganism, the medium, and the properties of the fermentationprocess (including, but not limited to, duration, medium temperature,medium pH, and medium oxygenation, among others). Also, one or morecompounds can be removed from the fermentation residues as a matter ofroutine experimentation by one of ordinary skill in the art. In variousembodiments, the fermentation residue comprises one or more compoundsselected from protein; glycerol; at least one organic acid; protein andglycerol; protein and at least one organic acid; glycerol and at leastone organic acid; or protein, glycerol, and at least one organic acid.

The fermentation residue can further comprise additional compounds,depending on the microorganism, the medium, and the properties of thefermentation process as described above. In the case of a yeast ethanolfermentation, the fermentation residue can further comprise any one ormore of fat, arabitol, sorbitol, trehalose, glucose, fructose,isomaltose, maltose, maltotriose, panose, chloride, sulfate, andphosphate, among other compounds. In the case of a yeast ethanolfermentation, the at least one organic acid can be any one or more oflactate, acetate, formate, pyruvate, succinate, and oxalate, among othercompounds.

In one embodiment, the fermentation residue comprises, by weight, fromabout 8 parts to about 11 parts protein, from about 0.01 parts to about0.04 parts fat, from about 6 parts to about 10 parts glycerol, fromabout 0.1 parts to about 0.4 parts arabitol, from about 0.1 parts toabout 0.8 parts sorbitol, from about 0.5 parts to about 1.2 partstrehalose, from about 0.9 parts to about 1.2 parts glucose, from about0.05 parts to about 0.10 parts fructose, from about 1.1 parts to about1.3 parts isomaltose, from about 0.1 parts to about 0.3 parts maltose,from about 0.01 parts to about 0.05 parts maltotriose, from about 0.07parts to about 0.30 parts panose, from about 0.01 parts to about 0.06parts linear 4-24 unit dextrose oligomers, from about 2 parts to about 4parts nonlinear 4-24 unit dextrose oligomers, from about 3 parts toabout 6 parts lactate, from about 0.1 parts to about 0.2 parts acetate,from about 0 parts to about 0.03 parts formate, from about 0.1 parts toabout 0.2 parts pyruvate, from about 0.4 parts to about 0.6 partschloride, from about 0.9 parts to about 1.1 parts succinate, from about0.5 parts to about 0.7 parts sulfate, from about 0.2 parts to about 0.3parts oxalate, and from about 2 parts to about 4 parts phosphate.

A typical fermentation residue comprises water-soluble compounds inaqueous solution. For such a composition, there is no particular lowerlimit on the concentration of water-soluble compounds in the solution.However, some minimal concentration of water-soluble compounds will beproduced in any typical fermentation. A typical minimum concentrationproduced by a typical fermentation, but one not to be construed aslimiting, is about 2 wt % water-soluble compounds. Also, one of ordinaryskill in the art will recognize that a particular fermentation residueintended for a particular application will have a certain minimumeconomically- and fimctionally-desirable concentration of water-solublecompounds. In one embodiment, the minimum concentration of water-solublecompounds in the fermentation residue is about 20 wt %. In anotherembodiment, the minimum concentration of water-soluble compounds in thefermentation residue is about 30 wt %. In still another embodiment, theminimum concentration of water-soluble compounds in the fermentationresidue is about 40 wt %.

Also, there is no particular upper limit on the concentration ofwater-soluble compounds in the fermentation residue. One of ordinaryskill in the art will recognize that a particular fermentation residueintended for a particular application will have a certain maximumconcentration of water-soluble compounds beyond which higherconcentrations may pose little, if any, economic or functional benefit.In one embodiment, the maximum concentration of water-soluble compoundsin the fermentation residue is about 60 wt %. In another embodiment, themaximum concentration of water-soluble compounds in the fermentationresidue is about 70 wt %. In still another embodiment, the maximumconcentration of water-soluble compounds in the fermentation residue isabout 80 wt %. In yet another embodiment, the maximum concentration ofwater-soluble compounds in the fermentation residue is about 90 wt %. Ina further embodiment, the maximum concentration of water-solublecompounds in the fermentation residue is about 100 wt %.

In any embodiment wherein the fermentation residue comprises at leastabout 90 wt % water-soluble compounds, the fermentation residue may bereferred to as a “dry” fermentation residue.

Depending on the particular fermentation residue and intendedapplication, any range of concentrations of the water-soluble compoundsis possible. Preferred ranges include all possible ranges defined by anyof the minimum concentrations and any of the maximum concentrationsdescribed above. In one embodiment, the fermentation residue comprisesfrom about 20 wt % to about 100 wt % water-soluble compounds. In anotherembodiment, the fermentation residue is dry.

Fermentation residues, as described above, possess utility as a concreteadmixture, either alone or with other admixtures. Admixtures are usedroutinely to improve the flow and setting properties in concrete.

Fermentation residues also possess utility in improving the flowproperties or dispersion of any inorganic material that is mixed inwater. One such material is gypsum mixed in water, the flow of which isimproved, which property would be useful to improve the productionprocess of wallboard (also known as drywall or gypsum panels, andcommercially available under the tradename Sheetrock®, USG Corporation,Chicago, Ill.).

Fermentation residues also possess utility in dispersing filler,pigment, or both in water for applications in paper manufacture andpaper coating operations.

Many of the embodiments of this invention, as described below, providesuperior flow properties in mixed concrete with a low cost additive.Better flow is beneficial to make concrete fill the gaps between rebarin roadways and is helpful when pumping concrete into forms.Additionally, improved flow allows less water to be used during mixingconcrete, thus typically resulting in stronger cured strength.

Similarly, in the production of wallboard, better flow allows less waterto be used during mixing, thus typically allowing reduced drying costsin the wallboard manufacturing process.

After the fermentation residue has been separated and, if desired,concentrated, the fermentation residue is combined with a cementitiousmaterial, to form a composition comprising a cementitious material and afermentation residue.

A “cementitious material,” as the term is used herein, is any materialwhich, when a dry powdered form thereof is wetted and allowed to set,will yield a rigid unitary solid. In one embodiment, the cementitiousmaterial is a cement. In another embodiment, the cementitious materialis gypsum. In a further embodiment, the cementitious material isselected from the group consisting of cements and gypsum.

In one preferred embodiment, the cementitious material is Type IPortland cement.

The composition comprising the fermentation residue and the cementitiousmaterial can be in any form. Typical forms include, but are not limitedto, a dry composition wherein the cementitious material, thefermentation residue, and other components are present in a homogeneousmixture of powdered ingredients (commonly termed a “premix”), such as iscommonly commercially available as a ready-mix cement, concrete, mortar,or grout, among others; a slurry wherein the cementitious material, thefermentation residue, and other components are mixed with water, such asis commonly prepared prior to pouring a cement, concrete, mortar, grout,drywall panel, among others; and a set composition, such as is formedafter a poured slurry is allowed to set. Any composition describedherein can be in any form described above or known to one of ordinaryskill in the art.

The composition can comprise fermentation residue water-solublecompounds and cementitious material in any weight ratio. However,certain weight ratios will provide compositions that are moreeconomical, have more desirable functional properties, or both. In oneembodiment, the minimum weight ratio of fermentation residuewater-soluble compounds to cementitious material is about 0.1 oz.fermentation residue water-soluble compounds per 100 pounds cementitiousmaterial. In another embodiment, the minimum weight ratio offermentation residue water-soluble compounds to cementitious material isabout 0.5 oz. fermentation residue water-soluble compounds per 100pounds cementitious material. In yet another embodiment, the minimumweight ratio of fermentation residue water-soluble compounds tocementitious material is about 1.0 oz. fermentation residuewater-soluble compounds per 100 pounds cementitious material.

In one embodiment, the maximum weight ratio of fermentation residuewater-soluble compounds to cementitious material is about 2.5 oz.fermentation residue water-soluble compounds per 100 pounds cementitiousmaterial. In another embodiment, the maximum weight ratio offermentation residue water-soluble compounds to cementitious material isabout 5.0 oz. fermentation residue water-soluble compounds per 100pounds cementitious material. In yet another embodiment, the maximumweight ratio of fermentation residue water-soluble compounds tocementitious material is about 10 oz. fermentation residue water-solublecompounds per 100 pounds cementitious material. In a further embodiment,the maximum weight ratio of fermentation residue water-soluble compoundsto cementitious material is about 20 oz. fermentation residuewater-soluble compounds per 100 pounds cementitious material. In yet afurther embodiment, the maximum weight ratio of fermentation residuewater-soluble compounds to cementitious material is about 50 oz.fermentation residue water-soluble compounds per 100 pounds cementitiousmaterial.

Depending on the particular fermentation residue, cementitious material,and intended application, among other parameters, any weight ratio offermentation residue water-soluble compounds to cementitious material ispossible. Preferred ranges include all possible ranges defined by any ofthe minimum weight ratios and any of the maximum weight ratios describedabove. In one preferred embodiment, the composition comprises from about0.1 oz. fermentation residue water-soluble compounds per 100 poundscementitious material to about 50 oz. fermentation residue water-solublecompounds per 100 pounds cementitious material. In another embodiment,the composition comprises from about 1 oz. fermentation residuewater-soluble compounds per 100 pounds cementitious material to about 20oz. fermentation residue water-soluble compounds per 100 poundscementitious material.

In one embodiment, a weight ratio of from about 1.0 oz. fermentationresidue water-soluble compounds per 100 pounds cement to about 7.0 oz.fermentation residue water-soluble compounds per 100 pounds cement issuitable for use in a Type “A” or Type “D” concrete admixture (AmericanSociety for Testing and Materials (ASTM) Standard C494 (WestConshohocken, Pa.)). In one embodiment, a weight ratio of from about 8.0oz. fermentation residue water-soluble compounds per 100 pounds cementto about 25.0 oz. fermentation residue water-soluble compounds per 100pounds cement is suitable for use in a Type “F” or Type “G” concreteadmixture (ASTM C494). Such concrete admixtures, as well as others thatwill be known to one of ordinary skill in the art, typically requireadditional components, such as water, aggregate, and in some cases,various additives. These additional components will be discussed below.

In addition to the fermentation residue and the cementitious material,at least one additional material can be added to the composition.

The composition may further comprise water in addition to any waterpresent in the fermentation residue. The composition can comprise waterwhen the composition is in a slurry (unset) form or in a set form. Whenthe composition is in a slurry form, the concentration of water,including both water present in the fermentation residue and water addedseparately to the composition (which may be referred to herein as “totalwater”), is typically reported as a water-cement ratio, defined as theweight of total water divided by the weight of the cementitiousmaterial. In one embodiment of a slurry form, particularly suitable forconcrete applications, the composition has a lower limit to thewater-cement ratio of about 0.25. In another embodiment of the slurryform, the composition has a lower limit to the water-cement ratio ofabout 0.3. In a further embodiment of the slurry form, the compositionhas a lower limit to the water-cement ratio of about 0.35.

In one embodiment of the slurry form, the composition has an upper limitto the water-cement ratio of about 0.75. In another embodiment of theslurry form, the composition has an upper limit to the water-cementratio of about 0.7. In a further embodiment of the slurry form, thecomposition has an upper limit to the water-cement ratio of about 0.65.

Depending on the particular fermentation residue, cementitious material,and intended application, among other parameters, any economically- andfunctionally-desirable water-cement ratio is possible for a slurry formof the composition. Preferred ranges for concrete applications includeall possible ranges defined by any of the minimum water-cement ratio andany of the maximum water-cement ratio described above. In one preferredembodiment of the slurry form, the composition has a water-cement ratiofrom about 0.25 to about 0.75.

The composition may further comprise an additive which imparts one ormore desirable properties to the composition, either in a dry form, aslurry, a set form, or two or more of the above. The additive cancomprise one active ingredient or a plurality of active ingredients, aswell as fillers, carriers, and other ingredients. In various preferredembodiments, the additive is selected from one of several groups whereineach group independently comprises one or more of flow improvers,plasticity improvers, water reducers, strengtheners, set retarders, setaccelerators, air entrainers, corrosion inhibitors, or shrinkcompensation agents. In one preferred embodiment, the additive isselected from the group consisting of a flow improver, a plasticityimprover, a water reducer, a strengthener, a set retarder, a setaccelerator, an air entrainer, and a shrink compensation agent.

The composition may comprise more than one additive. Desirably, eachadditive will be selected so as to not interfere with the functionalproperties of the fermentation residue, the cementitious material, andthe other additive or additives, if any.

Specific examples of additives useful in the composition include variousmaltodextrins containing from 1-100 dextrose equivalents (DE), such asStar-Dri 200 (a 20 DE maltodextrin made from normal corn starch) (A.E.Staley, Decatur, Ill.), setting accelerators such as triethanolamine(Sigma Chemical, St. Louis, Mo.), and RM35C and RM1000C (InternationalAdmixtures Inc., Boca Raton, Fla.). For such additives, as well as manyothers, the additive can be present at a wide range of concentrations.In one embodiment, the additive is present at at least about 5 wt %relative to fermentation residue water-soluble compounds. In anotherembodiment, the additive is present at at least about 10 wt % relativeto fermentation residue water-soluble compounds. In a furtherembodiment, the additive is present at at least about 15 wt % relativeto fermentation residue water-soluble compounds.

In one embodiment, the additive is present at no more than about 50 wt %relative to fermentation residue water-soluble compounds. In anotherembodiment, the additive is present at no more than about 40 wt %relative to fermentation residue water-soluble compounds. In a furtherembodiment, the additive is present at no more than about 30 wt %relative to fermentation residue water-soluble compounds.

In one preferred embodiment, the additive is present at from about 5 wt% to about 50 wt % relative to fermentation residue water-solublecompounds.

The composition may further comprise aggregate. Aggregate can be anymaterial suitable for bulking and strengthening. The inclusion ofaggregate distinguishes concrete from cement. Commonly used aggregatesinclude sand, gravel, crushed rock, and mixtures thereof, although anyaggregate known to one of ordinary skill in the art can be used. Sand iscommonly referred to as “fine aggregate,” and gravel, crushed rock, or amixture thereof is commonly referred to as “coarse aggregate.” Aggregatemay be a component of the composition when the composition is in a dry(premix) form, a slurry form, or a set form.

Any amount of aggregate suitable for the intended type of concrete to beprepared from a composition comprising the aggregate can be used. In oneembodiment, the aggregate is present at at least about 0.1 lbs/lbcementitious material. In another embodiment, the aggregate is presentat at least about 1 lb/lb cementitious material. In a furtherembodiment, the aggregate is present at at least about 4 lbs/lbcementitious material.

In one embodiment, the aggregate is present at no more than about 10lbs/lb cementitious material. In another embodiment, the aggregate ispresent at no more than about 8 lbs/lb cementitious material. In afurther embodiment, the aggregate is present at no more than about 6lbs/lb cementitious material.

In one preferred embodiment, the aggregate is present at from about 0.1lbs/lb cementitious material to about 10 lbs/lb cementitious material.In another preferred embodiment, the aggregate is present at from about4 lbs/lb cementitious material to about 6 lbs/lb cementitious material.

In various embodiments, the composition comprises one or more of atleast one additional material selected from water; aggregate; at leastone additive selected from the group consisting of flow improvers,plasticity improvers, water reducers, strengtheners, set retarders, setaccelerators, air entrainers, corrosion inhibitors, and shrinkcompensation agents; water and aggregate; water and at least oneadditive listed above; aggregate and at least one additive listed above;or water, aggregate, and at least one additive listed above.Alternatively or in addition to the above, further materials known toone of ordinary skill in the art may be added to the composition.

The order of addition of the various components of the composition isgenerally not crucial. However, water is generally only added as part ofthe process of forming a cementitious structure.

Upon the preparation of the composition comprising the fermentationresidue and the cementitious material, a slurry can be prepared, formed,and set to yield a cementitious structure.

By “cementitious structure” is meant any structure or structural elementwhich can be produced by the pouring and setting of a slurry comprisingwater and a cementitious material. After pouring and before setting, thestructure may be referred to as an “unset cementitious structure.” Aftersetting, the structure may be referred to as a “set cementitiousstructure.” Cementitious structures include foundations, floors, walls,slabs, construction panels, roads, bridges, mortar, grout, terrazo, andadhesive, among many others.

First, the water is added to the fermentation residue and thecementitious material, to yield a slurry. Further components which canbe combined with the fermentation residue, the cementitious material,and water include aggregate. Any aggregate as described above can beused. An additive, such as the additives described above, can also oralternatively be combined with the fermentation residue, thecementitious material, and water. The components, and any others thatmay be present, can be combined in any apparatus useful in containing,mixing, or allowing both to be performed on the components. Typically,the slurry is agitated to provide a homogeneous mixture and retardsetting until after an unset cementitious structure is formed.

Forming the slurry into an unset cementitious structure can be performedby any appropriate technique known in the art. As is well known in theart, forming typically involves pouring, spraying, or otherwiseintroducing the slurry into a mold, form, or other structure. Within thespace defined by the mold or form may be placed, prior to forming, anobject or material such as rebar for the purpose of enhancing thestrength or other structural properties of the set cementitiousstructure to be produced by the method.

Thereafter, the unset cementitious structure undergoes setting, to yieldthe cementitious structure. Setting proceeds by processes known in theart, and can be accelerated or retarded by the inclusion of variousadditives in the composition or by other processing techniques, as isknown in the art.

In another embodiment, the present invention relates to a composition,comprising:

a fermentation residue, water, and

an inorganic material dispersed in the water.

The fermentation residue and the water are as described above. Thefermentation residue may be prepared by separation from a microorganismbiomass and concentrating the water-soluble compounds of thefermentation residue, as described above.

By “inorganic material” is meant a material not comprising carbon. Inone embodiment, the inorganic material is a filler for paper manufactureor coating. In another embodiment, the inorganic material is a pigmentfor paper manufacture or coating. In a further embodiment, the inorganicmaterial is selected from the group consisting of paper fillers andpaper pigments.

Dispersal of the inorganic material in the water can be affected by anytechnique known in the art, such as dissolution, suspension, andemulsification, among others. Various of these techniques may call forfurther compounds, such as surfactants or emulsifiers, as will beapparent to one of ordinary skill in the art.

In another embodiment, the present invention relates to a method ofpreparing a composition comprising a fermentation residue, water, and aninorganic material dispersed in the water, the method comprising:

growing a microorganism on a medium, to form at least a microorganismbiomass and a fermentation residue;

separating the fermentation residue from the microorganism biomass; and

combining the fermentation residue with the water and the inorganicmaterial, to form the composition.

The growing and separating steps, and the compositions acted on oryielded by these steps, are essentially the same as those described inthe context of fermentation, above. The fermentation may result in theformation of one or more target products, and those compounds may beremoved prior to the separating step, as described above in the contextof fermentation. Also as described above, one or more compounds may bepartially or completely removed from the fermentation residue prior tothe combining step. In the combining step, the inorganic material is asdescribed above, and combining can be performed according to anyappropriate technique known in the art.

In another embodiment, the present invention relates to a method ofproducing a paper structure containing an inorganic material,comprising:

combining a fermentation residue with water and an inorganic material,to yield a solution;

treating the paper structure with the solution, to yield a treated paperstructure; and

removing water from the treated paper structure, to yield the paperstructure containing the inorganic material.

The solution comprising the fermentation residue, water, and theinorganic material is as described above, and combining can be performedby any appropriate technique.

The paper structure can be any structure comprising paper, paperboard,cardstock, cardboard, or any other material in any known form,including, but not limited to, printing paper, cartons, and cartonblanks, among others. The paper structure may contain materials otherthan the inorganic material, and these materials may be added before,after, or contemporaneously with the inorganic material added during theperformance of the method.

In the treating step, the paper structure is contacted with the solutionby any appropriate technique. Such techniques include, but are notlimited to, immersion of the paper structure in the solution, sprayingthe solution onto the paper structure or a surface thereof, and applyingthe solution via a brush or roller to the paper structure or a surfacethereof, among others. The duration of the treating step, as well as thetemperature of the solution and other relevant process parameters, canreadily be determined for a given application by one of ordinary skillin the art.

The treating step yields a paper structure comprising water, theinorganic material, and the fermentation residue. Thereafter, the wateris removed from the paper structure during the removing step. Removingwater can be performed by any appropriate technique that does not impairthe structure and physical properties of the paper structure. Suchtechniques include, but are not limited to, evaporation, includingevaporation assisted by heat, vacuum, or both, among others. By“removing,” in this context, is meant that at least about 90 wt % of allwater present in the portion of the solution present in the paperstructure after the treating step is eliminated from the paperstructure.

After removal of water, the paper structure comprises the inorganicmaterial and is suitable for further processing and use.

The following examples are included to demonstrate preferred embodimentsof the invention. It should be appreciated by those of skill in the artthat the techniques disclosed in the examples which follow representtechniques discovered by the inventor to function well in the practiceof the invention, and thus can be considered to constitute preferredmodes for its practice. However, those of skill in the art should, inlight of the present disclosure, appreciate that many changes can bemade in the specific embodiments which are disclosed and still obtain alike or similar result without departing from the spirit and scope ofthe invention.

EXAMPLES

The beneficial flow properties of beer still bottoms (BSB) filtrateconcentrate (a “fermentation residue” as defined above) are reportedbelow as observed in concrete mixing studies, mortar mixing studies, andin gypsum (wallboard) mixing studies.

Example 1 Pilot Scale Fractionation

Three 55-gallon drums of “raw” BSB were subjected to microfiltration.The configuration of the microfiltration apparatus was as follows:

Feed pump—Waukesha Model 60 with a VFD.

Circulation pump—Waukesha Model 220 (165 gpm)

Elements: 3 housings, in series, with 3 ceramic elements in each housing

#1 housing—1400 nm pore—Membralox

#2 housing—800 nm pore—Membra Flow

#3 housing—200 nm pore—Membra Flow

All elements had 6 mil lumen.

Each Element Area=0.36 m²

It took about 30 minutes to collect approximately 90 gallons of filtrate(˜210 L/m²/hr (LMH)). The yeast retentate was discarded. The filtratewas then processed on a drum scale evaporator in a pilot plant to bringthe dry solids level up to about 50%. It took 5 hours of evaporation togive 8 gallons of Concentrated BSB filtrate product.

The following evaporation conditions were found to work well: Steam 12psig Feed Pump 56-57% Extraction Pump 58-59% Vacuum 23 inches Hg ProductTemperature 140° F.

The following analytical results for Concentrated BSB filtrate wereobtained (Table 1): TABLE 1 Ash 8.56 % as is Moisture 54.57 % as isProtein 10.96 % as is Fat 0.03 % as is Glycerol 9.33 % as is Arabitol0.31 % as is Sorbitol 0.70 % as is Trehalose 1.14 % as is Glucose 0.93 %as is Fructose 0.09 % as is Iso-Maltose 1.21 % as is Maltose 0.25 % asis Maltotriose 0.02 % as is Panose 0.29 % as is Linear Highers(dp4-dp24) 0.01 % as is Non Linear Highers (dp4-dp24) 3.91 % as isLactate 5.21 % as is Acetate 0.19 % as is Formate 0.00 % as is Pyruvate0.12 % as is Chloride 0.52 % as is Succinate 0.99 % as is Sulfate 0.59 %as is Oxalate 0.28 % as is Phosphate 2.89 % as is

“Highers,” as the term is used herein, refers to dextrose oligomerscomprising from 4 to 24 dextrose units. “Linear highers” are dextroseoligomers that do not comprise branched or cyclic structures. “Nonlinearhighers” are dextrose oligomers comprising branched or cyclicstructures.

Example 2 Truckload Scale Fractionation

Microfiltration of 5,100 gallons of BSB (to remove the yeast bodies) wasaccomplished in about 4 hours at 150° F. The microfiltration apparatushoused ceramic membranes with an average pore size of 50 nm. Themicrofiltration was performed at a pressure of 38 psig, a feed flow rateof about 31 gpm, and a recirculation flow rate of about 11 gpm. Thisprocess produced 4,600 gallons of permeate at an average rate of 20 gpm(˜285 LMH).

Evaporation of the filtrate was completed in about 48 hours. At an earlystage of the evaporation, we applied 550 lb/hr of steam at a vacuum of18 inches of mercury. This resulted in an evaporation rate of about 400lb/hr of water at a temperature of 150° F. At a later stage of theevaporation, we increased the steam to 1,050 lb/hr at a vacuum of 22inches of mercury. This resulted in an evaporation rate of about 800lb/hr of water at a temperature of 134° F.

Heating for the evaporator was discontinued when the product refractiveindex (RI; measured at 40° C. on an Atago RX-500 refractometer, withdistilled water RI measured as 1.3307) reached 1.3907 to yield 280gallons of Concentrated BSB filtrate product at approximately 40% drysolids. The product was collected in five 55-gallon drums and one5-gallon pail.

The following analytical results for Concentrated BSB filtrate wereobtained (Table 2): TABLE 2 Ash 7.74 % as is Moisture 65.08 % as isProtein 8.36 % as is Fat 0.02 % as is Glycerol 6.52 % as is Arabitol0.18 % as is Sorbitol 0.18 % as is Trehalose 0.51 % as is Glucose 1.13 %as is Fructose 0.06 % as is Iso-Maltose 1.17 % as is Maltose 0.17 % asis Maltotriose 0.04 % as is Panose 0.08 % as is Linear Highers(dp4-dp24) 0.05 % as is Non Linear Highers (dp4-dp24) 2.88 % as isLactate 3.53 % as is Acetate 0.12 % as is Formate 0.02 % as is Pyruvate0.11 % as is Chloride 0.44 % as is Succinate 1.04 % as is Sulfate 0.59 %as is Oxalate 0.23 % as is Phosphate 3.01 % as is

It should be noted that chloride, sulfate, and phosphate from thisanalysis are double counted both under “ash” and in their own right.After taking this observation into account, greater than 99% of the massof the material is accounted for.

The majority of the Concentrated BSB Filtrate used in the followingexamples was taken from the batch whose analysis is shown above in Table2. The fermentation residue of Table 2 may be referred to herein as“O2-002.” Substantially all of the remaining Concentrated BSB Filtrateused in the examples was taken from a second batch, whose analysis wasgiven in Table 1.

Although a number of components of BSB differ in their levels betweenthe two batches, no significant difference in functional propertiesbetween the two batches was seen.

Example 3 Pilot Scale Study of Concentrated BSB Filtrate as a MortarAdmixture

A pre-weighed 1.0 kg portion of Portland cement (Type I, LaFarge Corp.,Hemdon, Va.) was placed in the bowl of a 5-quart mixer (Kitchen Aid,U.S.A., St. Joseph, Mich.). A 1.0 kg portion of sand was likewise addedto the mixer. Then 380 grams of water (or water including test agent)was added to the mixing bowl. The mixer was then switched on and allowedto mix at the lowest setting for 60 seconds. The water-cement ratio,defined as the weight of water divided by the weight of cement in themixture, was equal to 0.38 in this case (W/C=0.38).

Immediately after mixing was complete, a portion of the mortar wasplaced into a flow table cone. The cone was filled carefully to ensurethat voids were not introduced during filling and that the cone wascompletely filled and level at the top.

Next, the cone was carefully removed, and the diameter of the mortarpile was measured at three places around the circumference of the pilewith a caliper. The results were recorded and the average was reportedas the initial, or “0 drop,” flow in inches. Then one end of the droptable was lifted 1 inch above its resting position and allowed to dropfreely. This dropping action caused the mortar to flow out radially fromits initial position and the diameter of the mortar pile tended toincrease as a function of this vibration. A total of 5 drops wereperformed in succession, and the mortar pile was once again measured atthree places around the circumference of the pile with a caliper. Theresults were recorded and the average was reported as the “5 drop” flowin inches. Five more drops were then applied to the sample to give the“10 drop” flow in a similar manner. A greater diameter indicates greaterflow of the mortar pile.

After the flow test was complete, the remainder of the mortar mix wastransferred to a plastic container for a set-time assay. The materialwas “worked” a bit in the plastic container to ensure that no voids werepresent and that the material was evenly distributed in the container.The container was then transferred to a forced air oven set to 100° F.for the duration of the set-time assay. During this test, the sample wasperiodically removed from the oven and tested with a hand penetrometerfor its compressive strength. The set-time for this assay was defined asthe time it took for the mortar to reach a compressive strength of 500psi as determined with the penetrometer. Triplicate measurements weretaken and the average recorded about every 30 minutes until the endpointwas reached. More frequent measurements were taken near the endpoint sothat an accurate set-time could be determined. The final measurementsjust below and above the 500 psi target were used to interpolate thetime where a compressive strength of 500 psi was reached and this timewas recorded as the set-time for the experiment.

Typically, products were tested at a few levels of addition to evaluatethe “dose-response” relationship. Admixture preparations for mortar andconcrete are typically liquids with a dry solids content in the range of30 to 50% solids. The industry also tends to report admixture dosagesbased on fluid ounces per 100 pounds of cement in the formula. Both theconcentration of the admixture and the amount of admixture used relativeto the weight of cement in the mix must be defined to quantify theeffects of the active ingredients on the functional properties.

Usually a “no admix” control mortar sample was run for a baselinecomparison. Results from a recent test using O2-002 with quantitiesgiven as fl. oz. per 100 pounds cement are shown below (Table 3): TABLE3 0 drop 5 drop 10 drop set-time Admixture inches inches inches hours noadmix control 4.0 5.9 6.8 2.3 O2-002 @ 5 oz 5.1 6.7 7.7 3.3 O2-002 @ 10oz 5.2 6.8 7.8 4.2 O2-002 @ 15 oz 5.9 7.2 8.3 5.0

In this test, a dose dependent increase in flow was caused by the O2-002relative to the no admix control. A dose dependent retardation ofset-time due to the O2-002 was also seen in this study.

Example 4 Pilot Scale Study of Concentrated BSB Filtrate as a MortarAdmixture in Conjunction with Further Additives

In the next test, we investigated the effect of adding RM1000C (IAI,Boca Raton) to O2-002 on the flow properties of mortar. Two parts ofRM1000C were added to seven parts O2-002 in the test admixture. Theresults are shown in Table 4. An additional increase in flow was seenwith the addition of RM1000C to the O2-002. TABLE 4 dosage 0 drop 5 drop10 drop Admixture oz/100# inches inches inches no admix control 0 3.95.3 6.2 O2-002 10 5.3 6.6 7.5 15 6.0 7.5 8.1 20 6.1 7.8 8.7 O2-002 (withRM1000C) 10 6.6 8.1 9.1 15 6.7 8.4 9.5 20 6.6 8.4 9.5

Example 5 Pilot Scale Study of Concentrated BSB Filtrate as a MortarAdmixture in Conjunction with Further Additives

Another mortar study was performed to measure flow and set-time on awider range of doses for the O2-002/RM1000C (7:2) combination, andresults shown in Table 5, below. In this test, a dose dependent increasein flow was seen for the admixture. A dose dependent increase inset-time was seen up to a dose of 15 oz, then the trend reversed givingshorter set-times at higher doses. TABLE 5 dosage 0 drop 5 drop 10 dropset-time Admixture oz/100# inches inches inches hours no admix control 04.3 5.3 6.2 2.3 O2-002 5 5.9 6.9 7.6 3.6 (with RM1000C) 10 6.4 8.1 9.13.0 15 6.5 8.3 9.3 4.2 20 6.6 8.4 9.5 4.1 25 6.8 8.7 9.5 3.0

Example 6 Pilot Scale Study of Concentrated Molasses Solubles (CMS) as aMortar Admixture

A mortar study was performed on a different fermentation residue to showthe general utility of the present invention. Concentrated MolassesSolubles (CMS) is obtained from fermentation of Corynebacterium wherelysine is produced as the target product. After the target product isremoved by ion exchange chromatography, and the biomass is filtered off,the fermentation residue is evaporated to provide CMS. The CMS had thefollowing analysis: Total Nitrogen 6-7%  Ammonia Nitrogen 5% Phosphorous(P₂O₅) 0.2%   Potassium (K₂O) 0.2-0.4%     Sulfates 15-20%   Chlorides2% pH 4 to 5 Total Solids 42-46%  

In this example a mortar test was conducted to measure flow and set-timeon a range of admixture doses for the CMS (used “as is” at about 44%solids). Results are shown in Table 6, below. In this test, asignificant dose dependent increase in flow was seen for the CMSadmixture up to the 10 oz dose. A slight reduction in flow was seen at15 oz when compared to the 10 oz results. A dose dependent increase inset-time was seen up to a dose of 15 oz for the CMS. TABLE 6 dosage 0drop 5 drop 10 drop set-time Admixture oz/100# inches inches incheshours no admix control 0 4.1 5.8 6.8 2.4 Conc. Molasses 5 5.5 7.1 8.12.8 Solubles 10 5.7 7.6 8.6 3.2 15 4.7 7.2 8.4 3.8

Example 7 Pilot Scale Study of Concentrated BSB Filtrate as a ConcreteAdmixture in Conjunction with Further Additives

The concrete formula used in this test included 10.0 kg of Portlandcement (Type 1, LaFarge), 29.5 kg of coarse aggregate (¾″ stone), 24.3kg of fine aggregate (sand) and 5.5 kg of water (or water+admixture).This formula resulted in a water-cement ratio. of 0.55 (W/C=0.55).

The inside of a mixer was lightly moistened with water before initiatingmixing. The mixer was turned on, then 5.0 kg of water was added,followed by about half of the coarse aggregate and about half of thefine aggregate. Next, all of the cement was added a scoopful at a time.After the cement was mixed in over a few minutes, the remaining coarseand fine aggregate was added to the mixer. Finally, the last 0.5 kg ofwater (or water+admixture) was added and mixing was allowed to proceedanother 2.5 minutes.

Immediately after the concrete mixing was complete, a portion of theconcrete was transferred into a slump cone. The bottom third of theslump cone was filled, then subjected to twenty up and down strokes withan iron rod to ensure that voids were not introduced during filling. The“rodding” procedure was repeated after the cone was two-thirds full andalso when the cone was completely filled and level at the top.

Next, the slump cone was carefully removed, and the distance that theconcrete pile “slumped down” from its original height in the cone wasmeasured with a ruler and is reported as inches of slump.

After the slump test was complete, a portion of the concrete was passedthrough a #4 screen and transferred to a plastic container for theset-time assay. The material was “worked” a bit in the plastic containerto ensure that no voids were present and that the material was evenlydistributed in the container. The container was covered and allowed tosit at room temperature for the duration of the set-time assay. Duringthis test, the sample was periodically uncovered and tested with a handpenetrometer for its compressive strength. The set-time for this assaywas defined as the time it took for the mortar to reach a compressivestrength of 500 psi as determined with the penetrometer. Triplicatemeasurements were taken, and the average recorded, about every 30minutes until the endpoint was reached. More frequent measurements weretaken near the endpoint so that an accurate set-time could bedetermined. The final measurements just below and above the 500 psitarget were used to interpolate the time where a compressive strength of500 psi was reached and this time is recorded as the set-time for theexperiment.

The remainder of the concrete is transferred to plastic molds to makeconcrete cylinders for compressive strength testing. Twenty up and downstrokes with an iron rod were delivered to the concrete in the moldafter the mold was one-third, two-thirds, and completely filled. Themolds were capped with a plastic lid, then sent off to a concretetesting lab. The samples were typically tested for compressive strengthon 1, 3, 7, and 28 days after mixing. The average of duplicate (ortriplicate) tests are reported in units of psi.

Typically, products were tested at a few levels of addition to evaluatethe “dose-response” relationship. Admixture preparations for mortar andconcrete are typically liquids with a dry solids content in the range of30 to 50% solids. The industry also tends to report admixture dosagesbased on fluid ounces per 100 pounds of cement in the formula. Both theconcentration of the admixture and the amount of admixture used relativeto the weight of cement in the mix must be defined to quantify theeffects of the active ingredients on the functional properties. Usuallya “no admix” control concrete mix was run for a baseline comparison.Results from a test using O2-002 are shown below (Table 7): TABLE 7 7day 28 day slump set-time strength strength Admixture inches hours psipsi no admix control 1.9 3.5 5,527 7,039 O2-002 @ 7.5 oz 2.9 4.7 5,2006,367 O2-002 @ 15 oz 8.8 5.9 2,795 3,511 O2-002 (with RM1000C) @ 15 oz9.3 6.5 3,528 4,563

In this test, a dose dependent increase in slump was caused by theO2-002 relative to the no admix control. A dose dependent retardation ofset-time due to the O2-002 was also seen in this study. A dose dependentdecrease in strength was noted at 7 days and 28 days. Also in this testan additional ingredient, RM1000C (IAI, Boca Raton), was added to theO2-002. Blending RM1000C into the O2-002 admix gave improved results inthe slump and strength tests when compared to the results seen withO2-002 alone.

Example 8 Study of Concentrated BSB Filtrate as a Concrete Admixture inConjunction with Further Additives

A series of slump, set-time and strength measurements were performed onconcrete that had been treated with O2-002. Concrete was made with thetest admixtures at a W/C=0.53 and an ambient temperature ofapproximately 70° F.

Concrete made in this test had the following material usage per cubicyard: Cement (Type I Portland) 564 lbs. Coarse Aggregate (#57 Limerock)1656 lbs. Fine Aggregate (FDOT Concrete Sand) 1316 lbs. Water 298 lbs.

The test admixtures in this study were:

WRDA-64, a commercially available low range water reducing admixturemanufactured by the W. R. Grace Co.

O2-002 blended with RM35C (IAI, Boca Raton, 7:1 ratio), a low rangewater reducing admixture.

O2-002 with RM1000C (IAI, Boca Raton, 7:2 ratio), a high range waterreducing admixture.

Slump and set-time results from the independent testing are shown below(Table 8): TABLE 8 Dosage initial 30 min 45 min initial final oz/100#slump slump slump set time set time Admixture cement inches inchesinches hours hours WRDA-64 4 5.75 3 2.5 5.5 6.75 O2-002 5 8 5 3.5 4.756.25 (with RM35C) O2-002 8 5.75 4.5 3.75 5.25 6.5 (with RM35C) O2-002 106 2 1.75 7 9 (with RM35C) O2-002 10 8 5.75 4 8 9 (with RM1000C) O2-00215 10.25 8.25 5.5 10 12.5 (with RM1000C)

In this study, a dose dependent increase in slump was caused by theO2-002. A dose dependent retardation of set-time due to the O2-002 wasalso seen in this study. The low range water reducing admixturecontaining O2-002 at 5 oz compared favorably with the commerciallyavailable material WRDA-64 at 4 oz.

Compressive strength results from the independent testing are shownbelow (Table 9): TABLE 9 Dosage 3 day 7 day 28 day oz/100# strengthstrength strength Admixture cement psi psi psi WRDA-64 4 4,230 5,3706,573 O2-002 (with RM35C) 5 3,540 5,090 6,295 O2-002 (with RM35C) 8 n.tn.t n.t O2-002 (with RM35C) 10 n.t n.t n.t O2-002 (with RM1000C) 104,650 6,630 7,960 O2-002 (with RM1000C) 15 3,250 5,680 6,780

The strength table shows that the treatments gave quite similar resultswith a possible indication of improved strength for the O2-002 (withRM1000C) at a dose of 10 oz.

Example 9 Field Trial of Concentrated BSB Filtrate as a ConcreteAdmixture in Conjunction with Further Additives

A field trial was conducted at a ready-mix plant in order to assess theperformance of O2-002 as a concrete admixture under “real-life”conditions. The trial was conducted at a W/C=0.54 and an ambienttemperature of approximately 105° F.

Concrete made in this test had the following material usage per cubicyard: Cement (Type I Portland) 540 lbs. Coarse Aggregate (3/8″ RiverGranite) 1040 lbs. Fine Aggregate (River Sand) 1964 lbs. (contains 3%water) Water 233 lbs.

The only test admixture used in this study was O2-002 with RM1000C (IAI,Boca Raton, 7:2 ratio) as a high range water reducing admixture.

The admixture was used at a dosage of 10 oz/100 lb of cement (4.2gallons per 10 cubic yards). The initial slump was 8.5 inches, measured10 minutes after mixing. At the job site, the slump was measured at 7.5inches at 80 minutes after mixing. The batch continued to maintain agood plasticity even at 200 minutes after mixing, as it was pumped up tofill a second story beam loaded with rebar and completed the job withoutproblems. Even though the material showed remarkable plasticity,especially considering the high temperature at the job site, it hadbuilt enough strength to enable a crew to finish a floor poured from thebatch, with no difficulty, just 2 hours after pouring.

Example 10 Pilot Scale Study of Concentrated BSB Filtrate as anAdmixture in Gypsum Panel Production

For each sample, 75 grams of room temperature water (or water withadmixture) was added to a 600-mL stainless steel beaker. Then, 100 g drygypsum powder (National Gypsum Corporation, Charlotte, N.C.) was gentlypoured onto the water in the cup and a timer was started. A six-inch,stainless steel spatula was then used to gently push the gypsum underthe surface of the water (without stirring) over 10-20 seconds.

After allowing the gypsum to wet until 70 seconds had elapsed on thetimer, the slurry was vigorously mixed with the spatula for twentyseconds. When the timer showed 90 seconds had elapsed, the slurry waspoured through a glass funnel positioned in a ring stand. The lower,small mouth of the funnel was positioned three inches above a glassplate. The diameter of the poured gypsum patty was measured using largecalipers. The average of four measurements taken across the diameter ofthe patty was recorded.

After the gypsum patty had been poured onto the glass plate, the platewas moved under a ¼ lb. Gilmore needle. Elapsed time from the pouring ofthe patty was continuously monitored. The ¼ lb. Gilmore needle waslowered until the needle point just touched the gypsum patty, and thenthe needle was released. The force produced by the mass of the weightalone pushed the needle into the patty. When the ¼ lb. Gilmore needleonly penetrated the patty to a depth of 1 mm, the elapsed time frompouring was recorded as the set-time.

Results from a recent test using O2-002 are shown below (Table 10):TABLE 10 patty diameter set-time Admixture inches minutes no admixcontrol 3.5 4.58 O2-002 @ 0.3% 4.3 4.83 O2-002 @ 0.6% 4.6 6.58 O2-002 @1.2% 4.8 >10.00

In this test, a dose dependent increase in flow was caused by the O2-002relative to the no admix control. A dose dependent retardation ofset-time due to the O2-002 was also seen in this study.

Summary statistics for all runs of O2-002 in gypsum can be found below(Table 11): TABLE 11 patty diameter set-time inches minutes Admixturemean +/− SD mean +/− SD no admix control 3.77 +/− 0.17 4.48 +/− 0.14 (n= 5) O2-002 @ 0.3% 4.27 +/− 0.03 4.88 +/− 0.21 (n = 5) O2-002 @ 0.6%4.48 +/− 0.11 6.44 +/− 0.80 (n = 7) O2-002 @ 1.2% 4.63 +/− 0.12 >10.00(n = 7)

Example 11 Study of Particular Components of Concentrated BSB Filtrateas Mortar Admixture

In order to determine if a few of the high concentration ingredientsfound in O2-002 were mostly responsible for the activity seen in ourapplications testing, we tested both glycerol and lactic acidindividually for activity in our mortar and gypsum assays. In the mortarassay, we matched the concentration of glycerol and lactic acid (9.3%and 5.2%) respectively to that found in O2-002. Results are shown inTable 12. TABLE 12 Dosage 0 drop 5 drop 10 drop set-time Admixtureoz/100# inches inches inches hours no admix control 0 4.0 5.9 6.8 2.3glycerol 5 4.1 6.0 7.1 2.3 10 4.2 6.1 7.1 2.3 15 4.3 5.8 6.8 2.3 lacticacid 5 3.9 6.0 7.0 2.3 10 4.1 6.0 6.9 2.3 15 4.0 6.1 7.0 2.3 O2-002 55.1 6.7 7.7 3.3 10 5.2 6.8 7.8 4.2 15 5.9 7.2 8.3 5.0

The results show that individually, the glycerol and the lactic acidhave virtually no response difference from the “no admix” control. Theeffect of the O2-002 in this study was pronounced, and as expected.

Example 12 Pilot Scale Study of Concentrated BSB Filtrate and ParticularComponents Thereof as an Admixture in Gypsum Panel Production

A separate study in our gypsum assay is shown below, followingprocedures and using materials described below (Table 13): TABLE 13inclusion patty diameter set-time Admixture % inches minutes no admixcontrol 0.0 3.8 4.48 BSB “as is” 0.6 3.6 4.33 1.2 3.7 4.58 BSB retentate0.6 3.3 4.33 1.2 3.1 4.83 O2-002 (BSB permeate) 0.3 4.3 4.88 0.6 4.56.44 1.2 4.6 >10.00 glycerol 0.3 4.3 4.83 0.6 4.2 4.58 1.2 4.1 4.33lactic acid (50%) 0.3 4.3 4.83 0.6 4.2 5.58 1.2 4.4 7.3

In this study, we tested 50% stock solutions of BSB retentate (yeastfraction), glycerol, and lactic acid, in addition to BSB “as is”directly from the fermentor. We also used our O2-002 preparation (35%solids). The BSB “as is” results were not significantly different fromcontrol, while the BSB retentate results showed a decrease in flow.Glycerol showed an increase in flow compared to control but may haveshown an accelerated set at higher dose. Lactic acid paralleled theresults seen with O2-002 fairly closely, but it was tested at ten timesthe level at which it was found in O2-002 (50% vs. 5%).

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of this invention havebeen described in terms of preferred embodiments, it will be apparent tothose of skill in the art that variations may be applied to thecompositions and methods and in the steps or in the sequence of steps ofthe methods described herein without departing from the concept, spiritand scope of the invention as defined by the appended claims.

1. A composition, comprising: a cementitious material, and afermentation residue.
 2. The composition of claim 1, wherein thecementitious material is selected from the group consisting of cementsand gypsum.
 3. The composition of claim 2, wherein the cementitiousmaterial is Type I Portland cement.
 4. The composition of claim 1,wherein the fermentation residue is a yeast ethanol fermentation residueor a Corynebacterium lysine fermentation residue.
 5. The composition ofclaim 1, wherein the fermentation residue is prepared by growing amicroorganism on a medium, to form at least a microorganism biomass andthe fermentation residue, and separating the fermentation residue fromthe microorganism biomass.
 6. The composition of claim 5, wherein theseparating is performed by microfiltration with at least one membranehaving a pore size from about 50 nm to about 1500 nm.
 7. The compositionof claim 1, wherein the fermentation residue comprises from about 20 wt% to about 100 wt % water-soluble compounds.
 8. The composition of claim1, wherein the fermentation residue is dry.
 9. The composition of claim1, wherein the fermentation residue comprises protein, glycerol, and atleast one organic acid.
 10. The composition of claim 1, wherein thecomposition comprises from about 0.1 oz. fermentation residuewater-soluble compounds per 100 pounds cementitious material to about 50oz. fermentation residue water-soluble compounds per 100 poundscementitious material.
 11. The composition of claim 10, wherein thecomposition comprises from about 1 oz. fermentation residuewater-soluble compounds per 100 pounds cementitious material to about 20oz. fermentation residue water-soluble compounds per 100 poundscementitious material.
 12. The composition of claim 1, furthercomprising water other than any water present in the fermentationresidue.
 13. The composition of claim 12, wherein the water-cementweight ratio is from about 0.25 to about 0.75.
 14. The composition ofclaim 1, further comprising an additive selected from the groupconsisting of flow improvers, plasticity improvers, water reducers,strengtheners, set retarders, set accelerators, air entrainers,corrosion inhibitors, and shrink compensation agents.
 15. Thecomposition of claim 14, wherein the additive is present at from about 5wt % to about 50 wt % relative to fermentation residue water-solublecompounds.
 16. The composition of claim 1, further comprising aggregate.17. The composition of claim 16, wherein the aggregate is present atfrom about 0.1 lbs/lb cementitious material to about 10 lbs/lbcementitious material.
 18. The composition of claim 17, wherein theaggregate is present at from about 4 lbs/lb cementitious material toabout 6 lbs/lb cementitious material.
 19. The composition of claim 1,wherein the fermentation residue comprises, by weight, from about 8parts to about 11 parts protein, from about 0.01 parts to about 0.04parts fat, from about 6 parts to about 10 parts glycerol, from about 0.1parts to about 0.4 parts arabitol, from about 0.1 parts to about 0.8parts sorbitol, from about 0.5 parts to about 1.2 parts trehalose, fromabout 0.9 parts to about 1.2 parts glucose, from about 0.05 parts toabout 0.10 parts fructose, from about 1.1 parts to about 1.3 partsisomaltose, from about 0.1 parts to about 0.3 parts maltose, from about0.01 parts to about 0.05 parts maltotriose, from about 0.07 parts toabout 0.30 parts panose, from about 0.01 parts to about 0.06 partslinear 4-24 unit dextrose oligomers, from about 2 parts to about 4 partsnonlinear 4-24 unit dextrose oligomers, from about 3 parts to about 6parts lactate, from about 0.1 parts to about 0.2 parts acetate, fromabout 0 parts to about 0.03 parts formate, from about 0.1 parts to about0.2 parts pyruvate, from about 0.4 parts to about 0.6 parts chloride,from about 0.9 parts to about 1.1 parts succinate, from about 0.5 partsto about 0.7 parts sulfate, from about 0.2 parts to about 0.3 partsoxalate, and from about 2 parts to about 4 parts phosphate.
 20. A methodof preparing a composition comprising a cementitious material and afermentation residue, the method comprising: growing a microorganism ona medium, to form at least a microorganism biomass and a fermentationresidue; separating the fermentation residue from the microorganismbiomass; and combining the fermentation residue with the cementitiousmaterial, to form the composition.
 21. The method of claim 20, furthercomprising concentrating the fermentation residue water-solublecompounds prior to combining the fermentation residue with thecementitious material.
 22. The method of claim 20, wherein thecementitious material is selected from the group consisting of cementsand gypsum.
 23. The method of claim 20, wherein the microorganism isselected from the group consisting of yeast and Corynebacterium.
 24. Themethod of claim 20, wherein the separating is performed bymicrofiltration with at least one membrane having a pore size from about50 nm to about 1500 nm.
 25. The method of claim 20, wherein the growingstep further comprises producing at least one target product, and themethod further comprises removing the at least one target product fromthe medium, to retain the microorganism biomass and the fermentationresidue.
 26. The method of claim 25, wherein the at least one targetproduct is selected from the group consisting of ethanol and lysine. 27.The method of claim 20, further comprising removing one or morecompounds from the fermentation residue prior to the combining step. 28.The method of claim 20, further comprising combining the fermentationresidue and the cementitious material with at least one additionalmaterial selected from group consisting of water, aggregate, andadditives selected from the group consisting of flow improvers,plasticity improvers, water reducers, strengtheners, set retarders, setaccelerators, air entrainers, corrosion inhibitors, and shrinkcompensation agents.
 29. A method of producing a cementitious structure,comprising: combining at least a fermentation residue, a cementitiousmaterial, and water, to yield a slurry; forming the slurry into an unsetcementitious structure; and setting the unset cementitious structure, toyield the cementitious structure.
 30. The method of claim 29, whereinthe fermentation residue is a yeast ethanol fermentation residue or aCorynebacterium lysine fermentation residue.
 31. The method of claim 29,wherein the cementitious material is selected from the group consistingof cements and gypsum.
 32. The method of claim 29, wherein the combiningstep further comprises combining aggregate with the fermentationresidue, the cementitious material, and water.
 33. The method of claim29, wherein the cementitious structure is selected from the groupconsisting of foundations, floors, walls, slabs, construction panels,roads, mortar, grout, terrazo, and adhesive.
 34. A composition,comprising: a fermentation residue, water, and an inorganic materialdispersed in the water.
 35. The composition of claim 34, wherein thefermentation residue is prepared by growing a microorganism on a medium,to form at least a microorganism biomass and the fermentation residue,and separating the fermentation residue from the microorganism biomass.36. The composition of claim 35, wherein the separating is performed bymicrofiltration with at least one membrane having a pore size from about50 nm to about 1500 nm.
 37. The composition of claim 34, wherein theinorganic material is selected from the group consisting of paperfillers and paper pigments.
 38. A method of preparing a compositioncomprising a fermentation residue, water, and an inorganic materialdispersed in the water, the method comprising: growing a microorganismon a medium, to form at least a microorganism biomass and thefermentation residue; separating the fermentation residue from themicroorganism biomass; and combining the fermentation residue with thewater and the inorganic material, to form the composition.
 39. A methodof producing a paper structure containing an inorganic material,comprising: combining a fermentation residue with water and an inorganicmaterial, to yield a solution; treating the paper structure with thesolution, to yield a treated paper structure; and removing water fromthe treated paper structure, to yield the paper structure containing theinorganic material.